JPH04108196A - Sizing agent composition for paper making - Google Patents

Abstract

PURPOSE:To provide the subject sizing agent having a high sizing degree and exhibiting an excellent sizing property in a neutral to weekly acidic paper system by dispersing a specific resin and a copolymer (emulsifier polymer) in water in a specified solid content. CONSTITUTION:(A) 60-90 pts.wt. of a resin prepared by modifying (i) an esterification product of resin with an alkanol tertiary amine with (ii) an alpha,beta-unsaturated dibasic acid and (B) 1-40 pts.wt. of a copolymer (emulsifier polymer) of (iii) a cationic vinyl monomer with (iv) an aromatic vinyl monomer and/or a (meth)acrylic ester are dispersed in water in a solid content concentration of 20-60wt.% to provide the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a sizing agent for papermaking, and particularly to an internally added sizing agent that is extremely effective in neutral to weakly acidic papermaking.

BACKGROUND OF THE INVENTION Conventionally, rosin-based sizing agents have been widely used as paper sizing agents, and sulfuric acid bread earth has been used as an auxiliary agent. In this sizing agent, when the sulfuric acid bread earth dissociates, it becomes acidic, so paper sized with this system is acidic.

However, in recent years, the problem of acidic paper has become a topic of discussion, and there is a growing movement to make paper using neutral systems. By reducing the amount of sulfuric acid used, P
It is beginning to be widely practiced to make H closer to neutrality.

Furthermore, as the recovery rate of used paper increases and the use of closed systems for papermaking water progresses, the hardness of water has become significantly higher. In particular, waste paper contains calcium carbonate as a filler, which is one of the causes of increased water hardness. Furthermore, the papermaking temperature is often high.

Conventional rosin-based emulsion sizing agents mainly use anionic surfactants to stabilize dispersion, and in the above-mentioned systems, the sizing effect is significantly reduced. Therefore, in order to obtain the desired sizing degree, the amount of sizing agent used must be increased, but this not only increases costs due to the use of excessive sizing agent, but also causes problems such as foaming and pitch formation in the papermaking system. This causes operational inconvenience and also has a negative effect on paper quality.

Due to these circumstances, especially as a sizing agent for neutral paper,
Alkyl ketene dimer (AKD)-based and alkenyl succinic anhydride (ASA)-based sizing agents are widely used, or both AKD and ASA are sizing agents that are reactive with cellulose, so their stability varies. In particular, problems such as roll staining are likely to occur during operation. In addition, alkyl ketene dimers have weak rise-up size properties and still have problems such as paper slippage.

Therefore, in recent years, a rosin-based neutral sizing agent for papermaking has been proposed. Examples thereof include JP-A No. 54-11305, JP-A No. 60-161472, and JP-A No. 63-12.
It is known that it is described in Publication No. 0198 or the like.

The invention of JP-A No. 11305/1983 is a water solution prepared by copolymerizing styrene or its analogue with an aminoalkyl ester of (meth)acrylic acid in the presence of rosin acid. It is a dispersible or water-soluble polymer that has extremely excellent properties as a neutral sizing agent.

However, this product does not exhibit a size effect in the range where the amount of sizing agent added is low, resulting in high costs and its use is limited to special applications.

Note that in this specification, (meth)acrylic refers to acrylic and/or methacryl.

Furthermore, the invention described in JP-A-63-120198 discloses that the reinforced rosin, the (meth)acrylic acid alkyl ester and/or the styrene compound, and the (meth)acrylic acid alkylaminoalkyl ester and the alkylaminoalkyl amide. This is a rosin-based emulsion sizing agent consisting of a copolymer of the following, but it has difficulty in sizing in the neutral region, and cannot necessarily be said to be a sufficient sizing agent for neutral paper.

Furthermore, the invention described in JP-A-60-161472 is a sizing agent containing a rosin compound reinforced with an α,β-unsaturated unsaturated nylbonyl compound and esterified with a tertiary amino alcohol. . However, with the sizing agent specifically shown in this publication, it is not possible to obtain a good emulsion.

The present invention has been made in view of the above circumstances, and aims to obtain good size properties with good stability, particularly quick rise in the neutral region, and a means for solving the problems. Therefore, the present invention comprises 60 to 90 parts by weight of a resin obtained by modifying an esterification product of rosin and alkanol tertiary amines with α, β-, and β-dibasic acids, a cationic vinyl monomer, and an aromatic and 1-40 parts by weight of a copolymer (emulsifier polymer) with a monomer and/or a (meth)acrylic acid ester, dispersed in water at a solid content concentration of 20-60%. In the sizing agent of the present invention, the esterification reaction product of rosin and alkanol tertiary amines has a ratio of carboxyl groups of rosin to hydroxyl groups of alkanol tertiary amines (C
OOH: OH) is ○, 1 to 0.9, α, β-
The amount of β-dibasic acid added is preferably 2 to 12 parts by weight per 100 parts by weight of rosin.

Moreover, the emulsifier polymer in the present invention is 0.1 to 15 mol based on the cationic monomer, aromatic vinyl monomer, and/or (meth)acrylic acid ester.
Preferably, it is copolymerized in the presence of 6 amounts of rosin acid or α,β-unsaturated dibasic acid-added rosin acid.

The sizing agent of the present invention is prepared by dispersing a rosin derivative and an anti-drying agent polymer in water.

Examples of the basic rosin for rosin derivatives include camrosin, tall oil rosin, and wood rosin.

These rosins are then esterified with the alkanol tertiary amine. Examples of alkanol tertiary amines include triethanolamine, tripropazuramine,
Examples include triisopropaturamine, N-isobutylgetanolamine, and N-n-normalbutylgetanolamine.

This reaction can be carried out by heating and melting the rosin and adding the alkanol tertiary amine dropwise thereto. Alkanol grade for rosin? The amount of min added is
It is appropriate to set the ratio of the hydroxyl group of the alkanol tertiary amine to the carboxyl group of the rosin compound in the range of C0OH:0H=1:0.1-09.

The rosin esterified with the alkanol tertiary amine is then modified with an α,β-unsaturated dibasic acid. α,
Examples of β-unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and the like.

This reaction is carried out by esterifying the rosin in the step 1r described above, and then gradually adding an α,β-unsaturated dibasic acid. The amount of the α,β-unsaturated dibasic acid added is 2 to 12 parts by weight per 100 parts by weight of the rosin.
It is appropriate to use parts by weight.

Next, the emulsifier polymer is a copolymer of a cationic vinyl monomer and an aromatic vinyl monomer and/or a (meth)acrylic acid ester.

As the cationic vinyl monomer, a basic monomer having a tertiary amino group is suitable; examples thereof include:
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, dimethylaminoethyl (meth)
Examples include acrylamide, diethylaminoethyl (meth)acrylamide, dimethylaminepropyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide. Moreover, salts of these basic monomers and inorganic or organic acids can also be used.

Furthermore, it is also possible to use quaternary ammonium salts obtained by reacting the basic monomers with quaternizing agents such as methyl chloride, benzyl chloride, dimethyl sulfate, diethyl sulfate, epichlorohydrin, and dimethyldiallylammonium chloride. .

Further, as the aromatic vinyl monomer, styrene or a derivative thereof can be used. As a specific example,
Examples include styrene, α-methylstyrene, and vinyltoluene.

(Meth)acrylic acid ester is an ester of acrylic acid and/or methacrylic acid, and specific examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate,
Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 1-droxyethyl acrylate, 1-droxyethyl methacrylate,
Examples include hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

Either the aromatic vinyl monomer or the (meth)acrylic acid ester can be used, or both can be used in combination.

These cationic nyl monomers, aromatic nyl monomers, and 57' or (meth)acrylic acid esters are dissolved in a solvent, heated in the presence of a catalyst, and reacted to copolymerize.

After the reaction is completed, the solvent is distilled off, and water is added for water dispersion and water solubilization to obtain an emulsifier polymer.

In the emulsifier polymer, the cationic vinyl monomer, the aromatic vinyl monomer and/or the (meth)acrylic acid ester are contained in a proportion of 0.1 to 1 in proportion to the total amount thereof.
Preferably, the copolymerization is carried out in the presence of 5 mol 0° of rophosphoric acid or αβ-unsaturated dibasic acid-added rophosphoric acid.

Camrosin, wood rosin, )-lua-derived rosin, etc. can be used as the phosphoric acid, and α, β-
As the unsaturated dibasic acid-added rosin acid, maleated rosin, fumarated rosin, etc. can be used.

In the reaction of copolymerizing the emulsifier polymer, these rosin acids or α,β-unsaturated dibasic acid-added rosin acids are dissolved in the reaction system.

EXAMPLES The present invention will be described in detail below. In the following description, 'parts' means parts by weight unless otherwise specified.

Synthesis of Rosin Derivative Synthesis Example 1 100 parts of tall oil rosin (acid value 167) was heated to 210°C to melt it, and 105 parts of triethanolamine (CO
OH:0H=1:0.71) was added dropwise over 20+ hours.

The reaction was continued for 5 hours while keeping the temperature constant and dehydrating.

Then 9 parts of maleic anhydride were carefully added to the Xuma. After completing the addition of maleic anhydride, hold at the same temperature for 90 minutes,
Rosin derivative A was obtained. Its acid value was 94.

Synthesis Example 2 The amount of triethanolamine added was 2.3 parts (COOH:
Rosin derivative B was obtained in the same manner as in Synthesis Example 1, except that 0H=1:0.16) and the amount of maleic anhydride added was 4 parts. Its acid value was 156.

Synthesis Example 3 8 parts of N-n-n-butylgetanolamine (COOH: OH1:0.42) in place of triethanolamine
Rosin derivative C was obtained in the same manner as in Synthesis Example 1 except that the amount of maleic anhydride added was 8 parts. Its acid value was 146.

Synthesis Example 4 The amount of triethanolamine added was 5 parts <C0OH:0H
= 1 : 0.34) and rosin derivative DS- was obtained in the same manner as in Synthesis Example 1 except that 3 parts of fumaric acid was used in place of maleic anhydride.

Its acid value was 130.

Comparative Synthesis Example 7 parts of fumaric acid were dissolved in 93 parts of molten formaldehyde-treated tall oil rosin and maintained at 200°C for 3 hours to obtain rosin derivative E. Its acid value was 210.

Polymerization of emulsifier 1 polymer Polymerization example 1 10 equipped with stirrer, thermometer, reflux condenser and dropping funnel
10 parts of rosin and 100 parts of isopropyl alcohol were placed in a 0OCC four-bottle flask, and after sufficiently degassing with nitrogen gas, the temperature was raised to reflux temperature to dissolve the rosin. A mixed solution of 60 parts of styrene, 30 parts of dimethylaminoethyl methacrylate, and 2 parts of azobisisobutyronitrile was added dropwise to the mixture over 1 hour, and the mixture was allowed to react under reflux for 6 hours.

Next, continue heating and add about 70% isopropyl alcohol.
1 part was distilled off, and then a solution of 11 parts of acetic acid dissolved in 100 parts of water was added dropwise. The obtained aqueous dispersion is further heated,
The remaining isopropyl alcohol was distilled off. Next, 330 parts of water were added, 18 parts of epichlorohydrin was added thereto, 85 parts were reacted at 9°C for 1 hour, and water was added to obtain emulsifier polymer A with a solid content of 20%.

Polymerization Example 2 Into a 1000 cc four-loaf flask similar to that described in Polymerization Example 1, 61 parts of styrene, 15 parts of 2-ethylhexyl acrylate, and 70 parts of benzene were charged, and after sufficiently degassing with nitrogen gas, the mixture was heated to reflux temperature. The temperature was raised to While stirring, a solution of 2 parts of azobisisobutyronitrile dissolved in 30 parts of benzene was added dropwise over 1 hour.
Allowed time to react. Then, while continuing heating, add benzene to about 7
Distill 0 parts and add dropwise a solution of 9 parts of acetic acid dissolved in 100 parts of water. The resulting aqueous dispersion was further heated to completely distill off the remaining benzene.Then, 330 parts of water was added, and 14 parts of epichlorohydrin was added thereto to give 85 to 90% of the remaining benzene.
The reaction was carried out at 5° C. for 1 hour, and water was further added to obtain 20% emulsifier polymer B.

Polymerization Example 3 A fourth 100 OCC flask similar to that described in Polymerization Example 1 was charged with 20 parts of maleated rosin (8 parts of maleic anhydride, 92 parts of tall oil rosin as a reactant) and 100 parts of isopropyl alcohol, and decomposed with nitrogen gas. After cooling, the temperature was raised to reflux temperature and dissolved.

A mixture of 40 parts of styrene, 10 parts of n-butyl methacrylate, 30 parts of dimethylaminoethyl methacrylate, and 2 parts of azobisisobutyronitrile was added dropwise to this over an hour, and the mixture was reacted for 6 hours under reflux. While heating was continued, about 70 parts of isopropyl alcohol was distilled off, and then 11 parts of 5% N dissolved in 100 parts of water was added dropwise. The resulting aqueous dispersion was further heated until the remaining Isopropyl alcohol was completely distilled off.

Next, add 330 parts of water and add 1 part of epichlorohydrin.
8 parts were added, the reaction was carried out at 85 to 95°C for 1 hour, and water was further added to obtain an emulsion of 20°δ.

Polymerization Example 4 100 parts of isopropyl alcohol was charged into a 1000 cc four-neck flask similar to that described in Polymerization Example 1, and after thoroughly degassing with nitrogen gas, the temperature was raised to reflux temperature. To this, 60 parts of lauryl methacrylate, 40 parts of dimethylaminoethyl methacrylate, and 2 parts of azobisisobutyronitrile.
1 part of the mixed solution was added dropwise over 1 hour, and the mixture was allowed to react for 6 hours under reflux.

Next, add about 70% of isopropyl alcohol while continuing to heat.
1 part was distilled off, and a solution of 15 parts of acetic acid dissolved in 100 parts of water was added dropwise. The resulting aqueous dispersion was further heated to completely distill off the remaining isopropyl alcohol. Next, 330 parts of water was added, 24 parts of epichlorohydrin was added thereto, the mixture was reacted at 85 to 95°C for 1 hour, and water was further added to obtain 20% emulsifier polymer D.

Preparation Example 1 of Aqueous Dispersion 200 parts of rosin derivative A was dissolved in 200 parts of toluene,
200 parts of emulsifier polymer A (solid content: 40 parts) and 400 parts of ion-exchanged water were added and mixed at 40°C with a homomixer. Subsequently, this dispersion was transferred to a piston-type high-pressure emulsifier of 1 m (2 m)
A fine dispersion was obtained by passing it once through 0.00 to 9M>. Thereafter, toluene and some water were distilled off under reduced pressure to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion is
It was 3506.

Example 2 200 parts of rosin derivative B was dissolved in 200 parts of toluene,
52.5 parts of emulsifier polymer C (solid content: 105 parts) and 40 parts of ion-exchanged water were added and mixed in a homomixer at 40°C. Subsequently, this dispersion was passed once through a piston-type high-pressure emulsifier to obtain Kojimi JI-r powder, and toluene and some water were distilled off under reduced pressure to obtain an aqueous dispersion.

The solid content concentration of the obtained aqueous dispersion was 33%.

Example 3 200 parts of rosin derivative C was dissolved in 200 parts of toluene,
8429 parts of emulsifier polymer (solid content 86 parts) and 325 parts of ion-exchanged water were added and mixed in a homomixer at 40"C. Subsequently, this dispersion was transferred to a piston-type high-pressure emulsifier for 1 hour.
The mixture was passed through to obtain a partial dispersion of [41], and toluene and some water were distilled off under reduced pressure to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 33%.

Example 4 200 parts of rosin derivative D was dissolved in 200 parts of toluene,
334 parts of emulsifier polymer D (solid content: 67 parts) and 356 parts of ion-exchanged water were added and mixed at 40°C with a homomixer. Subsequently, this molecular P1 mixture was passed once through a piston-type high-pressure emulsifier to obtain a fine dispersion, and then toluene and some water were added to it under reduced pressure to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 34%.7 Example 5 200 parts of rosin derivative D was dissolved in 200 parts of toluene,
177 parts of emulsifier polymer C (solid content: 35.degree. 3 parts) and 407 parts of ion-exchanged water were added and mixed at 40.degree. C. with a homomixer. Subsequently, this dispersion was passed through a piston-type high-pressure emulsifier once to obtain a fine dispersion, and toluene and a small amount of water were added thereto to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 3,596.

Example 6 200 parts of rosin derivative A was dissolved in 200 parts of toluene,
6540 parts of emulsifier polymer (solid content: 108 parts) and 287 parts of ion-exchanged water were added and mixed in a homomixer at 40°C. Subsequently, this dispersion was passed once through a piston-type high-pressure emulsifier to obtain a soybean dispersion, and toluene and some water were added to the dispersion under reduced pressure to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 33%.

Actual Rejection 7 8200 parts of rosin derivative was dissolved in 200 parts of toluene,
Add 87 parts of emulsifier polymer A (solid content: 174 parts) and 438 parts of ion-exchanged water, and mix in a homomixer at 40'C.
mixed with. Subsequently, this dispersion was passed through a piston-type high-pressure emulsifier once to obtain a fine fraction Yi and a ladle, and toluene and some water were mixed under reduced pressure to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 33%.

Comparative Example 1 200 parts of rosin derivative E was dissolved in 200 m of toluene,
8111 parts of emulsifier polymer (solid content: 22.2 parts) and 430 parts of ion-exchanged water were added and mixed in a homomixer at 40°C. Subsequently, this dispersion was passed once through a piston-type high-pressure emulsifier to obtain a fine dispersion, and toluene and some water were mixed under reduced pressure to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 34%.

Comparative Example 2 93 parts of 0-syn derivative A were heated and melted at 180°C, and 13
While cooling at 0°ct and stirring, 4.8 parts of a 10% aqueous potassium hydroxide solution was slowly added, followed by a 10% aqueous casein solution (7 parts of casein and 189 parts of a 10% aqueous sodium hydroxide solution were dissolved in water). , the total amount was 70 parts) was gradually added. Additional hot water (95°C) 4
0 parts were gradually added dropwise to turn the emulsion into a 0/'W type, then 100 parts of hot water was added thereto, and the mixture was rapidly cooled to 30° C. to obtain an aqueous dispersion. The solid content concentration of the obtained aqueous dispersion was 31%.

The composition and stability of the aqueous dispersion were as shown in Table 1 Table 1 Test method Pulp L/NBKP (L:N=8:2) csf4201
A predetermined amount of calcium carbonate was added to the 2.5% pulp slurry and stirred. Cationic starch was added with stirring, and after stirring for 2 minutes, the aqueous dispersions of each example and comparative example were added as a sizing agent.

After 30 seconds, add a predetermined amount of liquid sulfuric acid bread soil, and add another 30 seconds.
After a few seconds, a polyacrylamide-based retention agent was added.

The pH of the slurry was adjusted by setting the amounts of calcium carbonate and sulfuric acid added to the pulp as shown in Table 2.

Table 3 After 30 seconds had passed since the slurry was prepared, hand paper (66 to 70 g/rr?) was prepared using a hand paper tester according to a conventional method. The obtained handmade paper was left in a constant temperature and humidity room at 20° C. and 165% for one day, and then subjected to a size test to measure the Steckigt sizing degree.

The test results are shown in Table 3.

Effects of the Invention As can be seen from Table 3, the present invention has a high degree of sizing, making it an excellent sizing agent. It exhibits excellent sizing properties, especially in neutral to weakly acidic papermaking systems.

Further, as shown in Table 1 above, the sizing agent of the present invention has a small average particle diameter and good storage stability.

Harima Kasei Co., Ltd.

Claims (1)

[Scope of Claims] 1. Resin 60~ which is obtained by modifying the esterification reaction product of rosin and alkanol tertiary amines with α,β-unsaturated dibasic acid.
90 parts by weight and 1 to 40 parts by weight of a copolymer (emulsifier polymer) of a cationic vinyl monomer and an aromatic vinyl monomer and/or (meth)acrylic acid ester are dispersed in water to obtain a solid content concentration of 20 to 60 parts by weight. Paper sizing agent composition 2, characterized in that the esterification reaction product of rosin and alkanol tertiary amines is expressed as a ratio of carboxyl groups of rosin to hydroxyl groups of alkanol tertiary amines (COOH:OH ) is 1:0.
1 to 0.9, and the amount of α,β-unsaturated dibasic acid added is 2 to 12 parts by weight per 100 parts by weight of rosin. Agent Composition 3 The emulsifier polymer contains 0.1 to 15 mol% of rosin acid or α,β-unsaturated diester based on the cationic vinyl monomer, aromatic vinyl monomer and/or (meth)acrylic acid ester. The paper sizing agent composition according to claim 1, which is copolymerized in the presence of a basic acid-added rosin acid.